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April 2l, 1942./` A R, NEvlTT 2,280,445

- PROCESS 0F TREATINGHYDROCARBONpILs Filed June 5, 1939 Il il ll 1N VENT OR. wmf-. www,

Patented Apr. 2l, i942 Unirernocnss or TREATG HYDnocAaoN Albert Ramsey Nevitt, Ne

signor to Bradford Penn Refining Corporation,

Clarendon, Pa.,

w Brunswick, N. as-

a corporation of Pennsylvania Application June 5, 1939, Serial No. 277,417

4 Claims.

The present invention relates to treatment of hydrocarbon oils and particularly to the conversion of ,crude petroleum oils Vof chemically complex character into synthetic hydrocarbons of less complex character and of a more stable as well as of amore useful nature. Special objects of the invention are to obtain sucha product Vthrough treatment of crude petroleum oils 'with a chemical reactive agent and Vaccelerating medium, which underrcertain conditions of temperature and'pressure will effect decomposition"'and' Vrecomposition of the crude petroleum into selective compounds.

A particularly important object of the invention is to accomplish the chemical conversion of petroleum oils containing large percentages of light hydrocarbons boiling within the gasoline and lighter constituent ranges into products of a more unsaturated character.

A further object of the invention is by suitable chemical treatment of crude petroleum oils of complex character containing approximately 40% of light constituents boiling within the gasoline range, to effect a combination of the lighter or the saturated undesirable constituents with the unsaturated portions, to form a stable viscous synthetic product, useful as a lubricating oil.

Other objects are to obtain from crude petroleum oils, increased yields of selective products desired, by wholly practical chemical treatment.

Additional objects and thevarious novel features of the invention will appear as the specification proceeds. Y

The drawing accompanying and forming part oi the following specification is a diagram or ow sheet illustration of the invention.

The invention involves the discovery that certain mixtures of metallic salts dissolved Vin an .excess acid solution together with metallic sulphate solutions, when injectedinto crudev petroleum, especiallyl those known as the paraiiin base oils,'found in Pennsylvania, under certain conditions of temperature and pressure, so that partial decomposition takes place, the bonds between the hydrocarbon structures will beruptured and a reforming of the molecular structure takes place, providing release and'back pressure be controlled to allow Vproper contactl time for the selective conversion.' f

It has long beenA known that .some of these hydrocarbons, especially those of the cyclic rings, such as the cyclo-parafns and cyclo-olefines undergo changes when subjected to thermal decompositionv andV vcondensation by heat. Such type of conversionlis termed soaking land the process known as polymerization The polymerization processes convert light products which are in the gaseousstate, into liquidand' solid constituents of different molecular structures. The liquid portion usually consists of a'miXture of polymers inthe benzene series and'boiling within the gasoline range. The solid portions contain peroXides and oxypolymers in the form of petroleum. gums, resins, asphaltic materials', anthracene in some cases and fixed carbon in the form of. coke, with liberation of hydrogen and methane. stituents also produces these hydrocarbons under cracking temperatures and at superatmospheric pressures.` l

In the rening off'paraihn base oils, under present known 'refining methods, the temperatures and 'pressures employed are usually below those required forccracking. This is an lessential factor due to the need of the rener to obtain the ,greatest possible yield of lubricantstfrom the crude and because such hydrocarbons easily undergo thermal decomposition, especially in the .presence of the lighter constituents boilingwithin the gasoline range and at superatmospheric pressure.

The paraiiin base oils while yielding the best quality lubricants, always contain large percentages of gasoline and paraffin waxes. The gasoline derived from such crudes, containing a large percentage of the paraflin hydrocarbons, is a rather inferior motor fuel, due to its low aromatic structure and high detonating characteristics when burned in modern high compression automobile engines. Such crudes usually contain about 30% to 40% of gasoline. The balance is made up of kerosene, gas oil, lubricants, wax and petrolatum, the two latter remaining in combination with the lubricants portion.v

The'lubricating portion is usually composed of the three fractions, non-viscous neutral oil, viscous neutral oil and cylinder stock. These fracf tions contain the wax and petrolatum portions, xl/arying in quantity usually from about 3% -to The Pennsylvania crudes with which this invention is primarily concerned, usually contain from about 3% to 51/2 of solids and semi-solids.

These substances are detrimental to the produc-y tion of quality lubricants. Their removal is difcult, requiring much separate processing, such as solvent treating, and the like.

Some processes have been devised for converting these solid and semi-solid constituents into cold settling and pressing rThe cracking of the heavier conother useful viscous liquid products which are then used for blending with the finished oils to back pressures, the latter' by way of general ex ample, being for instance, a back pressure of 150 improve their pour point characteristics. Cerlbs. per square inch, with a release pressure of tain of such methods have been quite successful about 40 to 60 lbs. per square inch. in producing high iiash viscous liquids which give 5 The aqueous vapors issuing from the release fluidity and pumpability to waxy oils, one such are subjected to gradual cooling and separation instance being that known as the manufacture and the resulting synthetic material is fracof Parafiow. tionated `into more or less conventional prod- Diculties and objections present in such ucts. processes have been the matters of expense re- As a specific example, a crude charging stock sulting from cost of extra-ction of the basic ma' from the Bradford District field of Pennsylvania terials, the cost of chemicals required for conwas used having the following specifications: version, the cost of process ltering and the loss ,L P. L Graw 43.1 of starting materials. These processes are bc- Color. .Green coming more and more impractical.' Originally, 15 Dfnatw o F. the basic materials required were v.by-products LHP. 70 and the processes were devised mainlyfor utili- 1g 12g zation of such by-products. The growing demand however, caused the rener to4 produceKV 40 360 them regularly, taking such materials out of the category of by-p-roductsand putting them in the 70 .522 class 'of manufactured specification products. 8010 0H In the Vpractice of such methods, temperatures summaryofcomponents and pressures used in distillation and fractiona- P t tion of the paraiiinic base oils have `been main- Gasoline 40o EPer cer;6 tained below those required forcracking, at tem- K ''ff "550 EP" n peratures vsuciently low to prevent cracking of Gerone s "660 EP" 18 the .lightest `lubricating constituent. This was ast because of .the fact that if temperature rises to 591,1 V15 tneltrl on "f" 4 the cracking point, decomposition of the lubri- C15' rtleia 1' ,79 eating fractions ensues, with consequent formary? ewa'x "1""- 1 5 tion of .light gasoline fractions `and production Cyhn er'sto'ck 14 of carbureted `gaseous compounds, which react Petr1atum` 2'5 againwith the heavier constituents to form fur- Loss '-f* 2 ther decomposition products in the nature of Gasvliegt in t 1Kr0Se@ cui benzene, gasoline and .low ash recycle stocks, A. P. I. om? c350 47.3 thecyclic hydrocarbons undergoing partial .poly- L BP- F merization into oxypolymers with much gum for- 10 15 '360 mation and carbon deposition. Increasing rpresgg sures .cause further :saturation and polymeriza- :40 40 200 ses tion, with subsequent loss of all lubricating can gg 32 ponentsof the crude. 10 245 `Study of the reactions occurring in the above mentioned methods has led tothe present in- 95 305 524 x'ention, whereinthe disadvantages are turned to 45 P- 399 '550 Other components as' con. M. P. aitls. Flash Fire Pour v Colora ,Sash V. I

Non vis. neutral 011 30,0 v350 .400 73 42 v30 1% .001 130 Via. neutral oi1 30.2 425 A85 -783 45.16 25 .3 .02 110 Crystalline wax. 42.0 ,i 211.3 oyunaeroii 25.9 550 020 150 .45 2,40 100 Petrolatum 32.0 550` 620 112 126.0

good vadvantage for vthe production of a syn- The 'chemical solutionwasprepared asfollows: thetic hydrocarbon, which `can be fractionated 60 400 grams ofcopper'sulphatexand 100 grams of Yto give increased yields of high quality wax free aluminum sulphate were'weighed out, thoroughly selective lubricants.l ground to tine-powder yand digested in 1000 cc. of

The invention involves a treatment consisting concentratedrhydrochloricacid. of subjecting a mixture of crude petroleum and Asecond;solution'was^made11pofreduced cobalt chemical solution to gradually increasing temlacetate y'15 grams, 4sodium nitrate 15 jgrams, soperature and pressure conditions up to a point dium vchloride 15 grams, digested in 1000 cc. of decomposition, according to analysis of the 'hydrochloriczacid charge and lproduct desired to obtain, then sub- The Ytwo lsolutions were mixed Atogether and jecting to temperature and pressure drop `in an j diluted with 1000 cc. concentrated hydrochloric enclosed zone andinjecting a further -quantity 7o acid and nltered. To this was then added 122 of Vchemicals and then increasing temperature kilogramsfofwater'at'60F. for a predetermined period, sufficient to effect Incarrying out `the treatment, with the appacomplete reaction. ratus illustrated, the vcrude oil landV thechemical -The contact 4time is an important `factor in compound'are transferredibpllmps |,.'"2.,'thr0u gh eiectingthe reaction --as are also the release and 7'5 the lines 3,1l,'to1a mixeri. 'Surgetanks 1,#in,

these `lines under pressure from airline 8, maintain a desired steady flow ofvv the materials; vQ By aninjectornozzle 9the chemical solution is injected direct into the ingoing crude oil. Before 3 'heating zone or at agbetween thesecondheating zone and-the iiashfch'amber, orA at both, or at otherpoints, the speed oil reaction -can`be retarded. Increasing the moisture content slows this mixture is effected, the chemical solution is 5 down the reaction, causing a lighterproduct to preferably heated to a temperature of 300 F. as be'formed, while decreasing the moisture content by means of a heater indicated at I0, pressure speedsup the reaction and causes a heavier and being suicient to' hold it in the liquid state, up to more viscous product to be formed. the injector nozzle. This nozzle preferably has a In the illustration, the finished synthetic prodrelatively small bore disposedV to allow the liquid to uctis iiashed a second time,fin the chamber 24, escape at high Velocity into the oil stream, thus to connected with the 'second heating zone by pipeiiect a thorough intermixing with the oil before ing 25. In this chamber, the product is lsettled entering the heating zone. hot to allow the spent metallic salts and sul- `From the mixer 5, the mixture passes by way of phides to settle and" be.- drawn off lthrough, the line Il', through the horizontally arranged series 15 line 20. From this flash chamber, the product of tubes I2, in the still I3, where it is subjected to passes overhead through line 2l, to a packed increasing temperatures up to, in the present bubble tower 28, and thence through fractionatillustration 860 F. and a contact time of 30 mining towers 29, 30 and cooler 3|, to storage at 32. utes at a pressure of about 225 lbs. per square inch. In this passage, the product is fractionated into This pressure is maintained through the medium more or less conventional commercial products. of a suitable pressure regulating 'valve or the like. In the illustration, the gravity is reduced from The heated mixture of oil and chemical solution 43.1 to 38. discharges through line III, under control of a A tabulation compiled from experimental runs pressure regulator Valve I5 into a flash chamber such as given by Way of example is here ap- IS, in an aqueous state. pended:

Breakdown of synthetic or reformed crude Say. vis. Synthetic Per cent Flash Fire Polgnm Color 94 38 Dark green.

` 2 00.1 16 41.3 10 38.4 1%. Non vis. neut 8 36. 2 2. Vis. neut l0 28. 4 4. Cylinder stock 54 27. 2 Dark green.

Entered in the central portion of the flash chamber is an injector nozzle I1, designed to inject at high velocity, a :further supply of chemicals to com-plete the reaction desired. This nozzle is supplied through lines 4, I8, under control o'f suitable valves. For some reactions, the second injection of chemicals may be unnecessary, in which case, such Valves would be entirely closed.

The temperature drop at the flash chamber I6, in the example under consideration, may be approximately 100 F., because of the location of such iiash chamber outside the heating zone and because of the influx of chemical solution at nozzle Il, which exchanges heat with the hot aqueous vapors entering the ash chamber.

The gaseous mixture passes from the flash chamber IB, by Way of line IS, through the vertically arranged series of tubes 20, forming the second heating zone, where decomposition temperatures in excess ci 1000 F. are maintained for a contact time of approximately 30 minutes, with a discharge pressure of about 45 to 60 lbs. per square inch and a back pressure, controlled by valve 2|, in excess of 100 lbs. per square inch.

In the present example, the chemical solution is injected in the mixer, for the rst heating zone at the rate of 240 grains per gallon of charging stock and at the flash chamber at the same rate oi 240 grains per gallon .of charge, making a total of 480 grains per gallon.

This, in the process described, eects a decomposition and a recomposition of the charge, producing a heavy synthetic viscous product, differing in characteristics from the starting materials.

By the injection of steam at diiferent points, such as at 22, between the mixer 5, and the first In the reactions outlined, the wax and petrolatum portions are converted to lubricating oil fractions, thus eliminating need for the customary filtering and dewaxing steps.

What is claimed is:

1. The process of treating hydrocarbon oils, which comprises subjecting a mixture of complex petroleum hydrocarbons and a chemically reactive solution containing metallic sulphates and chlorides to gradual heating and increasing pressure conditions on the order of up to 860 F. and 225 lbs. per square inch for a predetermined period .of time on the order of 30 minutes, flashing the mixture under controlled pressure conditions to reduce pressure and temperature, adding a further quantity of the reactive solution, subjecting the mixture to further gradual heating in excess of 1000 F. for a predetermined period of time on the order of 30 minutes, again flashing the mixture and hot settling the spent chemical solution and fractionating and cooling the treated hydrocarbon.

2. The process of treating hydrocarbon oils, which comprises subjecting a charging stock of petroleum hydrocarbon having a relatively high content of light constituents lower boiling than gas oil and higher boiling than normal hexane and a chemically reactive solution containing metallic sulphates and chlorides to gradual heating and increasing pressure conditions on the order of up to 860 F. and 225 lbs. persquare inch for a predetermined period of time on the order of 30 minutes, ashing the mixture under lcontrolled pressure conditions to reduce pressure and temperature, adding a further quantity of the reactive solution, subjecting the mixture to further gradual heating in excess of 1000 F. for

a predetermined period ,ofv time on the order of 30 minutes, again -iashing the -niixtnrev land. .hot settling the spent chemicalsolution and `fractionating and cooling the treated hydrocarbon.

3. The process of treatinghydrocarbon oils, which comprises subjecting a paraflle base petroleum hydrocarbon andia chemically reactive aqueous solutionfof metallic chlorides and soluble metallic sulphates toelevated temperature at superatmospheric pressure in an enclosure for a period of time sucient for partial decomposition ofthe hydrocarbon, hashing the mixture under controlled pressure conditions, separating out the spent chemical solution and fractionating and cooling the treated hydrocarbon.

:4. une process of treating hydrocarbon oils,

metallic `sulphates to 4elevated temperature at -superatmospheric pressure in an enclosure for a 4period otimesuicient-for partial decomposition of lthe hydrocarbon, flashing the mixture under controlled pressure conditions, injecting steam in reactive relation into ,the mixture at least at one point the 'passage of the mixture, separating fout ythe spent chemical solution and fractionating and cooling the treatedn hydrocarbon.

ALBERT'RAMSEY NEV'ITT. 

